CN111295603A - Light absorbing composition and optical filter - Google Patents
Light absorbing composition and optical filter Download PDFInfo
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- CN111295603A CN111295603A CN201880070437.9A CN201880070437A CN111295603A CN 111295603 A CN111295603 A CN 111295603A CN 201880070437 A CN201880070437 A CN 201880070437A CN 111295603 A CN111295603 A CN 111295603A
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- Prior art keywords
- wavelength
- light absorbing
- light
- group
- transmittance spectrum
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 138
- 230000003287 optical effect Effects 0.000 title claims description 165
- 239000000178 monomer Substances 0.000 claims abstract description 109
- 238000000411 transmission spectrum Methods 0.000 claims abstract description 87
- 238000002834 transmittance Methods 0.000 claims abstract description 77
- -1 phosphate ester Chemical class 0.000 claims abstract description 74
- 239000006096 absorbing agent Substances 0.000 claims abstract description 47
- 230000003595 spectral effect Effects 0.000 claims abstract description 46
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 36
- 239000010452 phosphate Substances 0.000 claims abstract description 36
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 35
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 45
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000003106 haloaryl group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000005027 hydroxyaryl group Chemical group 0.000 claims description 10
- 125000004999 nitroaryl group Chemical group 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 230000007423 decrease Effects 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 55
- 239000000243 solution Substances 0.000 description 53
- 239000000758 substrate Substances 0.000 description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- 229920005989 resin Polymers 0.000 description 27
- 239000011347 resin Substances 0.000 description 27
- 238000001228 spectrum Methods 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 238000003384 imaging method Methods 0.000 description 21
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 21
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 20
- 229920002050 silicone resin Polymers 0.000 description 20
- 239000007787 solid Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 19
- 238000002454 metastable transfer emission spectrometry Methods 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- 239000010419 fine particle Substances 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 13
- 239000011521 glass Substances 0.000 description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 12
- 150000001879 copper Chemical class 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000011342 resin composition Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 7
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- JFSDFUSYPBGANG-UHFFFAOYSA-N (2-bromophenyl)phosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1Br JFSDFUSYPBGANG-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229940078552 o-xylene Drugs 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000005368 silicate glass Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RRJHFUHAKCSNRY-UHFFFAOYSA-L [Cu+2].[O-]P([O-])=O Chemical compound [Cu+2].[O-]P([O-])=O RRJHFUHAKCSNRY-UHFFFAOYSA-L 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- UOKRBSXOBUKDGE-UHFFFAOYSA-N butylphosphonic acid Chemical compound CCCCP(O)(O)=O UOKRBSXOBUKDGE-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- PPKCVUUJHQNTLW-UHFFFAOYSA-N chlorooxy(phenyl)phosphinic acid Chemical compound ClOP(=O)(O)C1=CC=CC=C1 PPKCVUUJHQNTLW-UHFFFAOYSA-N 0.000 description 2
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- RCMHUQGSSVZPDG-UHFFFAOYSA-N phenoxybenzene;phosphoric acid Chemical class OP(O)(O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 RCMHUQGSSVZPDG-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AQSYSSDRYRRQKN-UHFFFAOYSA-N (2,3-dichlorophenyl)phosphonic acid Chemical compound OP(O)(=O)C1=CC=CC(Cl)=C1Cl AQSYSSDRYRRQKN-UHFFFAOYSA-N 0.000 description 1
- SAAVRBVATZLIEH-UHFFFAOYSA-N (2,3-difluorophenyl)phosphonic acid Chemical compound OP(O)(=O)c1cccc(F)c1F SAAVRBVATZLIEH-UHFFFAOYSA-N 0.000 description 1
- MTNQLAKBYRCDTF-UHFFFAOYSA-N (2-nitrophenyl)phosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1[N+]([O-])=O MTNQLAKBYRCDTF-UHFFFAOYSA-N 0.000 description 1
- XDGIQCFWQNHSMV-UHFFFAOYSA-N (4-bromophenyl)phosphonic acid Chemical compound OP(O)(=O)C1=CC=C(Br)C=C1 XDGIQCFWQNHSMV-UHFFFAOYSA-N 0.000 description 1
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 description 1
- OGBVRMYSNSKIEF-UHFFFAOYSA-N Benzylphosphonic acid Chemical compound OP(O)(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-N 0.000 description 1
- POJIUOGMSBGKHH-UHFFFAOYSA-N BrC(C1=CC=CC=C1)(P(O)(O)=O)Br Chemical compound BrC(C1=CC=CC=C1)(P(O)(O)=O)Br POJIUOGMSBGKHH-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PFHCGFQWNRNHDE-UHFFFAOYSA-N O[P+](O)([O-])c1cccc(Br)c1Br Chemical compound O[P+](O)([O-])c1cccc(Br)c1Br PFHCGFQWNRNHDE-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- UQMARDZPRCIGET-UHFFFAOYSA-N [bromo(phenyl)methyl]phosphonic acid Chemical compound OP(O)(=O)C(Br)C1=CC=CC=C1 UQMARDZPRCIGET-UHFFFAOYSA-N 0.000 description 1
- FKKZWEWQUQIZKF-UHFFFAOYSA-N [chloro(phenyl)methyl]phosphonic acid Chemical compound OP(O)(=O)C(Cl)C1=CC=CC=C1 FKKZWEWQUQIZKF-UHFFFAOYSA-N 0.000 description 1
- LGNPNZUMCOLGJC-UHFFFAOYSA-N [dichloro(phenyl)methyl]phosphonic acid Chemical compound OP(O)(=O)C(Cl)(Cl)C1=CC=CC=C1 LGNPNZUMCOLGJC-UHFFFAOYSA-N 0.000 description 1
- LEHCDHHLEVYQNS-UHFFFAOYSA-N [difluoro(phenyl)methyl]phosphonic acid Chemical compound OP(O)(=O)C(F)(F)C1=CC=CC=C1 LEHCDHHLEVYQNS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- WYKCOLQQHSQKIU-UHFFFAOYSA-L copper butyl-dioxido-oxo-lambda5-phosphane Chemical compound [Cu++].CCCCP([O-])([O-])=O WYKCOLQQHSQKIU-UHFFFAOYSA-L 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- DHGSSULXZRNIPW-UHFFFAOYSA-L copper;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Cu+2].[O-]P([O-])(=O)C1=CC=CC=C1 DHGSSULXZRNIPW-UHFFFAOYSA-L 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000005303 fluorophosphate glass Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Optical Filters (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The light absorbing composition of the present invention contains a light absorbing agent comprising a prescribed phosphonic acid and copper ions, and an alkoxysilane monomer for dispersing the light absorbing agent, and does not contain a phosphate ester having a polyoxyalkyl group. The light absorbing composition contains an alkoxysilane monomer in order that the normalized transmittance spectrum has a wavelength band having a spectral transmittance of 70% or more at a wavelength of 300nm to 700nm and the difference between the maximum value and the minimum value of the wavelength in the wavelength band is 100nm or more.
Description
Technical Field
The present invention relates to a light absorbing composition and a light filter.
Background
In an imaging Device using a solid imaging element such as a CCD (Charge Coupled Device) or a CMOS (complementary metal Oxide Semiconductor), various filters are arranged in front of the solid imaging element in order to obtain an image with good color reproducibility. In general, a solid-state imaging element has spectral sensitivity in a wide wavelength range from an ultraviolet region to an infrared region. On the other hand, the human visual acuity exists only in the region of visible light. Therefore, in order to make the spectral sensitivity of a solid-state imaging element in an imaging device close to the human visual sensitivity, a technique is known in which a filter for shielding infrared rays or ultraviolet rays is disposed in front of the solid-state imaging element.
As such an optical filter, there are an optical filter utilizing light reflection by a dielectric multilayer film and an optical filter having a layer containing a light absorbing agent. The latter filter is advantageous in view of reducing the incident angle dependence of light of the optical characteristics of the filter.
For example, patent document 1 describes a near-infrared cut filter formed of a near-infrared absorbent and a resin. The near-infrared absorber is obtained from a prescribed phosphonic acid compound, a prescribed phosphate ester compound and a copper salt. The specified phosphonic acid compounds having a radical-CH bonded to the phosphorus atom P2CH2-R11A monovalent group R1。R11Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 20 carbon atoms. The phosphate ester compound has a structure consisting of- (CH) bonded to a phosphorus atom P via an oxygen atom2CH2O)nR5Monovalent group (polyoxyalkyl) as shown. R5Is an alkyl group having 6 to 25 carbon atoms or an alkylphenyl group having 6 to 25 carbon atoms. According to patent document 1, it is considered that a copper phosphonate salt obtained by reacting a predetermined phosphonic acid compound with a copper salt is kept in an extremely fine state by the action of a predetermined phosphate ester compound.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-
Disclosure of Invention
Problems to be solved by the invention
According to the technique described in patent document 1, a phosphate ester compound having a polyoxyalkyl group is required in order to maintain a copper phosphonate salt in a very fine state in a near infrared ray absorbent.
Accordingly, the present invention provides a light absorbing composition in which a light absorbing agent composed of phosphonic acid and copper ions is dispersed in spite of not containing a phosphate compound having a polyoxyalkyl group, and which is advantageous in imparting desired optical characteristics to a filter. Further, the present invention provides an optical filter which can exhibit desired optical characteristics even though it does not contain a phosphate compound having a polyoxyalkyl group.
Means for solving the problems
The present invention provides a light absorbing composition comprising:
a light absorber formed of a phosphonic acid represented by the following formula (a) and copper ions; and
an alkoxysilane monomer for dispersing the above light absorbing agent,
does not contain a phosphate ester having a polyoxyalkyl group,
the alkoxysilane monomer is contained so that the normalized transmittance spectrum has a wavelength band having a spectral transmittance of 70% or more at a wavelength of 300 to 700nm and the difference between the maximum value and the minimum value of the wavelength in the wavelength band is 100nm or more,
the normalized transmittance spectrum described above is obtained as follows: the normalized transmittance spectrum is obtained by obtaining a transmittance spectrum by vertically allowing light having a wavelength of 300nm to 1200nm to enter a light absorbing layer formed by drying and humidifying a film of the light absorbing composition, and normalizing the transmittance spectrum so that the spectral transmittance at a wavelength of 700nm is 20%.
[ CHEM 1 ]
[ in the formula, R11Is an alkyl group, an aryl group, a nitroaryl group, a hydroxyaryl group, or a haloaryl group in which at least 1 hydrogen atom in the aryl group is substituted with a halogen atom.]
The present invention also provides an optical filter comprising a light absorbing layer containing a light absorbing agent comprising a phosphonic acid represented by the following formula (a) and copper ions and a hydrolyzed polycondensate of alkoxysilane monomers, and containing no phosphate ester having a polyoxyalkyl group,
the normalized transmittance spectrum has a first wavelength band having a spectral transmittance of 70% or more at a wavelength of 300nm to 700nm, and the difference between the maximum value and the minimum value of the wavelength in the first wavelength band is 100nm or more,
the normalized transmittance spectrum described above is obtained as follows: the normalized transmittance spectrum is obtained by obtaining a transmittance spectrum by allowing light having a wavelength of 300 to 1200nm to enter the filter perpendicularly, and normalizing the transmittance spectrum so that the spectral transmittance at a wavelength of 700nm is 20%.
[ CHEM 2 ]
[ in the formula, R11Is an alkyl group, an aryl group, a nitroaryl group, a hydroxyaryl group, or a haloaryl group in which at least 1 hydrogen atom in the aryl group is substituted with a halogen atom.]
ADVANTAGEOUS EFFECTS OF INVENTION
The light absorbing composition described above does not contain a phosphate ester compound having a polyoxyalkyl group, but is advantageous in that a light absorbing agent composed of phosphonic acid and copper ions is dispersed, and that desired optical characteristics are imparted to the optical filter. The optical filter described above can exhibit desired optical characteristics even though it does not contain a phosphate compound having a polyoxyalkyl group.
Drawings
Fig. 1 is a cross-sectional view showing an example of the optical filter of the present invention.
Fig. 2 is a cross-sectional view showing another example of the optical filter of the present invention.
Fig. 3 is a cross-sectional view showing another example of the optical filter of the present invention.
Fig. 4 is a cross-sectional view showing another example of the optical filter of the present invention.
Fig. 5 is a cross-sectional view showing an example of the imaging optical system of the present invention.
Fig. 6 is a normalized transmittance spectrum of the filter of example 1.
Fig. 7 is a normalized transmittance spectrum of the filter of example 2.
Fig. 8 is a normalized transmittance spectrum of the filter of example 10.
Fig. 9 is a normalized transmittance spectrum of the filter of comparative example 2.
Fig. 10 is a normalized transmittance spectrum of the filter of example 11.
FIG. 11 is a normalized transmittance spectrum of the filter of example 12.
FIG. 12 is a normalized transmittance spectrum of the filter of example 14.
Fig. 13 is a normalized transmittance spectrum of the filter of comparative example 3.
FIG. 14 is a normalized transmittance spectrum of the filter of example 16.
FIG. 15 is a normalized transmittance spectrum of the filter of example 18.
Fig. 16 is a normalized transmittance spectrum of the filter of example 20.
FIG. 17 is a normalized transmittance spectrum of the filter of example 22.
FIG. 18 is a normalized transmittance spectrum of the filter of example 24.
FIG. 19 is a normalized transmittance spectrum of the filter of example 34.
FIG. 20 is a normalized transmittance spectrum of the filter of example 35.
Fig. 21 is a normalized transmittance spectrum of the filter of example 50.
Detailed Description
The inventor considers that: the phosphate ester in the technique described in patent document 1 has a polyoxyalkyl group, and therefore is likely to be hydrolyzed when exposed to water, and is hardly considered to be an optimal material in terms of weather resistance. In the technique described in patent document 1, it is considered that if a sufficient amount of resin is present together with the near infrared ray absorber, the weather resistance of the near infrared ray cut filter is at a level that does not pose a problem, but a relatively large amount of resin is required. Thus, the inventors also believe that: according to the technique described in patent document 1, the thickness of the near-infrared cut filter is easily increased. Accordingly, the present inventors have continuously conducted repeated studies on new materials suitable for dispersing a light absorber formed of prescribed phosphonic acid and copper ions. As a result, the present inventors have innovatively found that the light absorbing agent can be appropriately dispersed even when an alkoxysilane monomer is used instead of a phosphate ester having a polyoxyalkyl group. The present inventors have studied the light absorbing composition and the optical filter of the present invention based on this new technical idea.
Hereinafter, embodiments of the present invention will be described with reference to the drawings. The following description relates to an example of the present invention, and the present invention is not limited to these descriptions.
The light absorbing composition of the present invention contains a light absorber and an alkoxysilane monomer. The light absorber is formed from phosphonic acid represented by the following formula (a) and copper ions. The alkoxysilane monomer disperses the light absorber. In addition, the light absorbing composition does not contain a phosphate having a polyoxyalkyl group. In addition, the light absorbing composition contains an alkoxysilane monomer so that the normalized transmittance spectrum has a wavelength band having a spectral transmittance of 70% or more at a wavelength of 300nm to 700nm and a difference between a maximum value and a minimum value of the wavelength in the wavelength band is 100nm or more, in other words, the kind and amount of the alkoxysilane monomer in the light absorbing composition are determined so that the normalized transmittance spectrum has a wavelength band having a spectral transmittance of 70% or more at a wavelength of 300nm to 700nm and a difference between a maximum value and a minimum value of the wavelength in the wavelength band is 100nm or more. Thus, an optical filter manufactured using the light absorbing composition easily has desired optical characteristics. The normalized transmittance spectrum is obtained as follows: the normalized transmittance spectrum is obtained by obtaining a transmittance spectrum by vertically allowing light having a wavelength of 300nm to 1200nm to enter a light absorbing layer formed by drying and humidifying a film of the light absorbing composition, and normalizing the transmittance spectrum so that the spectral transmittance at a wavelength of 700nm is 20%.
[ CHEM 3 ]
[ in the formula, R11Is an alkyl group, an aryl group, a nitroaryl group, a hydroxyaryl group, or a haloaryl group in which at least 1 hydrogen atom in the aryl group is substituted with a halogen atom.]
In the light absorbing composition, the light absorbing agent is dispersed appropriately by the action of the alkoxysilane monomer, although the phosphate ester having a polyoxyalkyl group is not contained. In addition, an optical filter can be produced using the light absorbing composition. In this case, hydrolysis reaction and polycondensation reaction of the alkoxysilane monomer contained in the light absorbing composition occur, and a siloxane bond (-Si-O-Si-) is formed. In other words, a hydrolyzed condensate of alkoxysilane monomer is produced. The hydrolyzed polycondensate of alkoxysilane monomer has a prescribed functional group which enters between the light absorbers to cause steric hindrance, and prevents aggregation of the light absorbers. Thus, the light absorbing composition of the present invention can impart desired optical characteristics to the optical filter even though it does not contain a phosphate ester compound having a polyoxyalkyl group.
The phosphate ester having a polyoxyalkyl group is not particularly limited, and examples thereof include Plysurf a 208N: polyoxyethylene alkyl (C12, C13) ether phosphate, Plysurf a 208F: polyoxyethylene alkyl (C8) ether phosphate, Plysurf a 208B: polyoxyethylene lauryl ether phosphate, Plysurf a 219B: polyoxyethylene lauryl ether phosphate, Plysurf AL: polyoxyethylene styrenated phenyl ether phosphate, Plysurf a 212C: polyoxyethylene tridecyl ether phosphate, or PlysurfA 215C: polyoxyethylene tridecyl ether phosphate. These are all products manufactured by the first industrial pharmaceutical company. Examples of the phosphate ester include NIKKOL DDP-2: polyoxyethylene alkyl ether phosphate, NIKKOL DDP-4: polyoxyethylene alkyl ether phosphate, or NIKKOL DDP-6: polyoxyethylene alkyl ether phosphate ester. These are all products manufactured by Nikkol Chemicals.
The light absorbing composition is preferably substantially free of (i) other compounds having a polyoxyethylene alkyl group, (ii) compounds having a sulfonic acid group or a sulfate ester group which exert an effect of facilitating dispersion of the light absorbing agent by addition, and (iii) compounds containing an amine salt or a quaternary ammonium salt. The light absorbing composition can prevent aggregation of the light absorbing agent even though it does not contain such a compound.
The alkoxysilane monomer preferably contains an alkyl group-containing alkoxysilane monomer represented by the following formula (b). In this case, when a hydrolyzed polycondensate of the alkoxysilane monomer is formed, the alkyl group of the alkyl group-containing alkoxysilane monomer enters between the light absorbers, and aggregation of the light absorbers can be more reliably prevented.
(R2)n-Si-(OR3)4-n(b)
[ in the formula, R2Is an alkyl group having 1 to 4 carbon atoms, R3Is an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 3.]
The alkoxysilane monomer is not particularly limited as long as the normalized transmittance spectrum satisfies the above conditions, and includes, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, or 3-glycidoxypropylmethyldiethoxysilane.
The phosphonic acid of the formula (a) is not particularly limited, as in R11In the case of a phosphonic acid which is an alkyl group (alkyl phosphonic acid), the alkyl group is, for example, a phosphonic acid having an alkyl group of 1 to 8 carbon atoms. At R11In the case of a phosphonic acid (aryl phosphonic acid) which is an aryl, nitroaryl, hydroxyaryl or haloaryl group, the phosphonic acid represented by formula (a) is, for example, phenylphosphonic acid, nitrophenylphosphonic acid, hydroxybenzenePhenylphosphonic acid, bromophenylphosphonic acid, dibromophenylphosphonic acid, fluorophenylphosphonic acid, difluorophenylphosphonic acid, chlorophenylphosphonic acid, dichlorophenylphosphonic acid, benzylphosphonic acid, bromobenzylphosphonic acid, dibromobenzylphosphonic acid, fluorobenzylphosphonic acid, difluorobenzylphosphonic acid, chlorobenzylphosphonic acid, or dichlorobenzylphosphonic acid.
The supply source of copper ions in the light absorbing composition is, for example, a copper salt. The copper salt is, for example, copper acetate or a hydrate of copper acetate. The copper salt may be an anhydride or hydrate of copper chloride, copper formate, copper stearate, copper benzoate, copper pyrophosphate, copper naphthenate, and copper citrate. For example, copper acetate monohydrate is represented as Cu (CH)3COO)2·H2O, 1 mole of copper ions was supplied through 1 mole of copper acetate monohydrate.
The relationship between the content of phosphonic acid and the content of copper ions and the content of alkoxysilane monomer in the light absorbing composition is not particularly limited as long as the normalized transmittance spectrum satisfies the above-described conditions. For example, the ratio of the content of the alkoxysilane monomer to the content of the copper ion is 2.0 or more, preferably 2.5 or more on a substance basis. The ratio of the content of the alkyl group-containing alkoxysilane monomer of formula (b) in which n is 1 or 2 to the content of copper ions is, for example, 1.5 or more on a substance basis.
For example, when the following conditions (α 1) and (β 1) are satisfied, the ratio of the content of the alkyl group-containing alkoxysilane monomer of formula (b) in which n is 1 or 2 to the content of copper ions is 2.5 or more on the basis of the substance amount.
(α 1) the phosphonic acid comprises R in formula (a)11Phosphonic acid which is an aryl, nitroaryl, hydroxyaryl, or haloaryl in which at least 1 hydrogen atom of the aryl group is substituted with a halogen atom.
(β 1) the alkoxysilane monomer includes an alkyl group-containing alkoxysilane monomer of formula (b) in which n is 1 or 2, and a tetrafunctional alkoxysilane monomer of formula (c).
Si-(OR4)4(c)
[ in the formula, R4Is an alkyl group having 1 to 8 carbon atoms.]
When the following conditions (α 2) and (β 2) are satisfied, for example, the ratio of the content of the alkyl group-containing alkoxysilane monomer of formula (b) in which n is 1 or 2 to the content of copper ions is 3.0 or more on a substance basis, and in this case, an optical filter produced using the light absorbing composition tends to have desired optical characteristics.
(α 2) the phosphonic acid comprises R in formula (a)11Phosphonic acid which is an aryl, nitroaryl, hydroxyaryl, or haloaryl in which at least 1 hydrogen atom of the aryl group is substituted with a halogen atom.
(β 2) the alkoxysilane monomer includes an alkyl group-containing alkoxysilane monomer of formula (b) in which n is 1 or 2, and does not include the tetrafunctional alkoxysilane monomer of formula (c).
When the following conditions (α 3) and (β 3) are satisfied, for example, the ratio of the content of the alkyl group-containing alkoxysilane monomer having n of 1 or 2 to the content of copper ions in the formula (b) is 1.5 or more on a substance basis.
(α 3) the phosphonic acid comprises only R of formula (a)11Phosphonic acids that are alkyl.
(β 3) the alkoxysilane monomer includes an alkyl group-containing alkoxysilane monomer of formula (b) in which n-1 or 2.
The light absorbing composition may further contain a resin as necessary, or may not contain a resin in some cases. In the light absorbing composition, the ratio of the content of the solid content of the resin composition to the sum of the content of the phosphonic acid, the content of the copper ion and the content of the alkoxysilane monomer in terms of the hydrolyzed polycondensate is, for example, 0 to 3.0, preferably 0 to 2.7 on a mass basis. Thus, the amount of the resin used in the light absorbing composition is small, and thus the thickness of the optical filter manufactured using the light absorbing composition is likely to be small.
When the light absorbing composition further contains a resin, the resin is not limited to a specific resin, and is, for example, a silicone resin, as long as the normalized transmittance spectrum satisfies the above-described conditions. The silicone resin is a compound having a siloxane bond (-Si-O-Si-) in its structure. In this case, since the hydrolyzed condensate of alkoxysilane monomer also has siloxane bonds, the hydrolyzed condensate of alkoxysilane monomer derived from alkoxysilane monomer has good compatibility with resin in the optical filter.
The resin is preferably a silicone resin containing an aryl group such as a phenyl group. If the resin contained in the optical filter is hard (rigid), cracks are likely to occur due to curing shrinkage in the manufacturing process of the optical filter as the thickness of the layer containing the resin increases. If the resin is a silicone resin containing an aryl group, the layer formed from the light absorbing composition tends to have good crack resistance. In addition, the silicone resin containing an aryl group has high compatibility with the phosphonic acid represented by formula (a), and the light absorber is difficult to aggregate. Specific examples of the silicone resin used as the matrix resin include KR-255, KR-300, KR-2621-1, KR-211, KR-311, KR-216, KR-212, KR-251 and KR-5230. They are all silicone resins manufactured by shin-Etsu chemical industries, Inc.
The light absorber in the light absorbing composition is formed, for example, by complexing copper ions with phosphonic acid represented by formula (a). In addition, for example, fine particles including at least a light absorbing agent are formed in the light absorbing composition. In this case, as described above, the fine particles are dispersed in the light absorbing composition without being aggregated with each other by the action of the alkoxysilane monomer. The average particle diameter of the fine particles is, for example, 5nm to 200 nm. If the average particle diameter of the fine particles is 5nm or more, a special step for micronization of the fine particles is not required, and the structure of the fine particles including at least the light absorbing agent is less likely to be destroyed. In addition, in the light absorbing composition, the fine particles are well dispersed. When the average particle diameter of the fine particles is 200nm or less, the influence of mie scattering can be reduced, the transmittance of visible light in the filter can be increased, and the deterioration of characteristics such as contrast and haze of an image captured by an imaging device can be suppressed. The average particle diameter of the fine particles is preferably 100nm or less. In this case, since the influence of rayleigh scattering is reduced, the transparency of the filter made of the light absorbing composition to visible light is improved. The average particle diameter of the fine particles is more preferably 75nm or less. In this case, the optical filter manufactured using the light absorbing composition has particularly high transparency to visible light. The average particle size of the fine particles can be measured by a dynamic light scattering method.
An example of a method for producing the light absorbing composition of the present invention will be described. For example, the light-absorbing composition contains R in the formula (a)11In the case of a phosphonic acid (aryl phosphonic acid) which is an aryl group, a nitroaryl group, a hydroxyaryl group, or a haloaryl group in which at least 1 hydrogen atom in the aryl group is substituted with a halogen atom, liquid D is prepared as follows. A copper salt such as copper acetate monohydrate is added to a predetermined solvent such as Tetrahydrofuran (THF) and stirred to prepare a solution a as a copper salt solution. Next, the aryl phosphonic acid is added to a predetermined solvent such as THF and stirred to prepare solution B. When two or more kinds of aryl phosphonic acids are used as the phosphonic acid represented by formula (a), solution B can be prepared by adding each aryl phosphonic acid to a predetermined solvent such as THF and stirring the mixture, and mixing a plurality of kinds of preliminary solutions prepared for each kind of aryl phosphonic acid. For example, an alkoxysilane monomer is added in the preparation of the liquid B. While stirring the solution A, the solution B was added to the solution A and stirred for a predetermined time. Then, a predetermined solvent such as toluene is added to the solution and stirred to obtain a solution C. Then, the solution C is heated and desolventized for a predetermined time to obtain a solution D. Thus, the light absorber is produced by removing components generated by dissociation of a copper salt, such as a solvent such as THF and acetic acid (boiling point: about 118 ℃ C.), using phosphonic acid represented by the formula (a) and copper ions. The temperature at which the solution C is heated is determined based on the boiling point of the component to be removed dissociated from the copper salt. In the solvent removal treatment, a solvent such as toluene (boiling point: about 110 ℃ C.) used for obtaining the solution C is also volatilized. The solvent preferably remains in the light-absorbing composition to some extent, and therefore the amount of the solvent to be added and the time for the solvent removal treatment can be defined from this point of view. In order to obtain liquid C, o-xylene (boiling point: about 144 ℃ C.) may be used instead of toluene. In this case, the boiling point of o-xylene is higher than that of toluene, so that the boiling point of o-xylene can be higher than that of tolueneSo as to reduce the addition amount to about one fourth of the addition amount of toluene.
The light absorbing composition contains R in the formula (a)11In the case of a phosphonic acid (alkyl phosphonic acid) which is an alkyl group, for example, liquid H is prepared as follows. First, a copper salt such as copper acetate monohydrate is added to a predetermined solvent such as Tetrahydrofuran (THF) and stirred to obtain a solution E as a copper salt solution. Further, an alkyl phosphonic acid is added to a predetermined solvent such as THF and stirred to prepare a solution F. When two or more kinds of phosphonic acids are used as the alkyl phosphonic acid, the respective alkyl phosphonic acids may be added to a predetermined solvent such as THF and stirred, and a plurality of kinds of preliminary solutions prepared for each kind of alkyl phosphonic acid may be mixed to prepare solution F. For example, an alkoxysilane monomer is further added in the preparation of the F liquid. While stirring the solution E, the solution F was added to the solution E and stirred for a predetermined time. Then, a predetermined solvent such as toluene is added to the solution and stirred to obtain solution G. Then, the solution G is heated and desolventized for a predetermined time to obtain a solution H. Thus, components generated by dissociation of the copper salt, such as a solvent such as THF and acetic acid, are removed. The temperature for heating the solution G is determined in the same manner as the solution C, and the solvent for obtaining the solution G is also determined in the same manner as the solution C.
For example, the light absorbing composition can be prepared by mixing the solution D and the solution H at a predetermined ratio and adding a resin such as a silicone resin if necessary. In some cases, the light absorbing composition may be prepared by adding a resin such as a silicone resin to either of the D liquid and the H liquid. The D liquid and the H liquid may be used individually as the light absorbing composition.
Next, the optical filter of the present invention will be explained. As shown in fig. 1 to 4, optical filters 1a to 1d as examples of the optical filter of the present invention include an optical absorption layer 10. The light absorbing layer 10 contains a light absorbing agent formed of a phosphonic acid represented by the above formula (a) and a copper ion, and a hydrolysis polycondensate of alkoxysilane monomers, and does not contain a phosphate ester having a polyoxyalkyl group. In the filters 1a to 1d, the normalized transmittance spectrum has a first wavelength band having a spectral transmittance of 70% or more at wavelengths of 300nm to 700 nm. The difference between the maximum value and the minimum value of the wavelength in the first wavelength band is 100nm or more. The normalized transmittance spectrum is obtained as follows: the normalized transmittance spectrum is obtained by obtaining transmittance spectra by causing light having a wavelength of 300nm to 1200nm to enter the filters 1a to 1d perpendicularly, and normalizing the transmittance spectra so that the spectral transmittance at a wavelength of 700nm is 20%.
Although the optical filters 1a to 1d do not contain a phosphate ester having a polyoxyalkyl group, the light absorbing agent is appropriately dispersed in the optical filters 1a to 1d by the action of the hydrolyzed condensate of the alkoxysilane monomer. Therefore, the normalized transmittance spectrum satisfies the above-described condition. Further, since the hydrolyzed condensate of the alkoxysilane monomer has a siloxane bond (-Si-O-Si-), the light absorbing layer 10 is moderately hard and excellent in heat resistance, and is less likely to be deteriorated even when exposed to water, and thus is also excellent in weather resistance. In the filters 1a to 1d, the normalized transmittance spectrum satisfies the above-described conditions, and thus the filters 1a to 1d have high spectral transmittance in a wide range of the visible light region. The hydrolyzed condensate of alkoxysilane monomer has a structure similar to that of silicate glass and thus has high transparency to visible light, which also advantageously helps the normalized transmittance spectrum to satisfy the above-mentioned conditions.
Examples of the phosphate ester having a polyoxyalkyl group include, but are not limited to, Plysurf a 208N: polyoxyethylene alkyl (C12, C13) ether phosphate, Plysurf a 208F: polyoxyethylene alkyl (C8) ether phosphate, Plysurf a 208B: polyoxyethylene lauryl ether phosphate, Plysurf a 219B: polyoxyethylene lauryl ether phosphate, Plysurf AL: polyoxyethylene styrenated phenyl ether phosphate, Plysurf a 212C: polyoxyethylene tridecyl ether phosphate, or PlysurfA 215C: polyoxyethylene tridecyl ether phosphate. These are all products manufactured by the first industrial pharmaceutical company. Examples of the phosphate ester include NIKKOL DDP-2: polyoxyethylene alkyl ether phosphate, NIKKOL DDP-4: polyoxyethylene alkyl ether phosphate, or NIKKOL DDP-6: polyoxyethylene alkyl ether phosphate ester. These are all products manufactured by Nikkol Chemicals.
In the filters 1a to 1d, the normalized transmittance spectrum preferably has a second wavelength band having a spectral transmittance of 80% or more at wavelengths of 300nm to 700 nm. The difference between the maximum value and the minimum value of the wavelength in the second band is 40nm or more. In this case, the filters 1a to 1d have desired optical characteristics in the visible light region.
In the filters 1a to 1d, the normalized transmittance spectrum preferably has a third wavelength band having a spectral transmittance of 20% or less at a wavelength of 700nm to 1200 nm. The difference between the maximum value and the minimum value of the wavelength in the third wavelength band is 120nm or more. In this case, the filters 1a to 1d can appropriately block light having a predetermined wavelength band of 700nm to 1200 nm. Therefore, the filters 1a to 1d have desired optical characteristics at wavelengths of 700nm to 1200 nm.
In the filters 1a to 1d, the normalized transmittance spectrum preferably has a fourth wavelength band and a fifth wavelength band. The fourth wavelength band is a wavelength band in which the spectral transmittance decreases with increasing wavelength. The fifth wavelength band is a wavelength band including wavelengths shorter than the minimum value of the wavelengths in the fourth wavelength band, and is a wavelength band in which the spectral transmittance increases with an increase in the wavelength. The spectral transmittance in the fourth wavelength band shows that the first cut-off wavelength, which is a wavelength of 50%, exists in the range of 600nm to 650 nm. The light transmittance in the fifth wavelength band shows that the wavelength of 50%, i.e., the second cutoff wavelength, exists in the range of 350nm to 420 nm. The difference obtained by subtracting the second cut-off wavelength from the first cut-off wavelength is 200nm to 290 nm. In this case, the filters 1a to 1d can block light of a specific wavelength, and have optical characteristics advantageous for example to be disposed in front of the solid-state imaging element. In this specification, the first cut-off wavelength and the second cut-off wavelength are also referred to as an IR cut-off wavelength and a UV cut-off wavelength, respectively.
In the normalized transmittance spectra of the filters 1a to 1d, it is preferable that the maximum wavelength which is a wavelength showing the maximum spectral transmittance is in the range of 500nm to 550 nm. In addition, the wavelength exhibiting the minimum spectral transmittance at a wavelength of 700nm to 1200nm, that is, the extremely small wavelength, is in the range of 750nm to 900 nm. In addition, the difference obtained by subtracting the maximum wavelength from the minimum wavelength is 240nm to 360 nm. In this case, the minimum wavelength and the maximum wavelength in the normalized transmittance spectrum are in preferable ranges, and the filters 1a to 1d have desired optical characteristics.
In the normalized transmittance spectra of the filters 1a to 1d, the difference obtained by subtracting the minimum spectral transmittance at a wavelength of 700nm to 1200nm of the normalized transmittance spectra from the maximum spectral transmittance at the normalized transmittance spectra is preferably 68% or more. In this case, the difference is sufficiently large for the filters 1a to 1d to have desired optical characteristics. The difference is preferably 70% or more.
In the optical filters 1a to 1d, the light absorbing layer 10 is typically formed by subjecting a film of the above light absorbing composition to a drying treatment and a humidifying treatment. As a result, the alkoxysilane monomer contained in the light absorbing composition undergoes hydrolysis and polycondensation reactions, and changes to a hydrolysis polycondensate.
An example of a method for producing the light absorbing layer 10 will be described. For example, the light absorbing composition is applied to a predetermined substrate by a method such as spin coating or application using a dispenser to form a coating film, and the coating film is heated and dried. For example, the coating film is exposed to an environment at a temperature of 50 ℃ to 200 ℃. Next, the dried coating film is subjected to a humidification treatment in order to sufficiently promote the hydrolysis reaction and the polycondensation reaction of the alkoxysilane monomer. For example, the dried coating film is exposed to an environment having a temperature of 50 ℃ to 100 ℃ and a relative humidity of 60% to 100%. Thus, a repeating structure of siloxane bond (Si-O) is formedn. Thus, the light absorbing layer 10 is produced. The maximum value of the atmospheric temperature of the coating film in the drying treatment is, for example, 85 ℃ or higher, from the viewpoint of improving the optical characteristics of the optical filters 1a to 1d while firmly forming the light absorbing layer 10. The conditions for the humidification treatment of the coating film are not particularly limited as long as they are conditions capable of sufficiently promoting the hydrolysis reaction and the polycondensation reaction of the alkoxysilane monomer, and for example, the humidification treatment of the coating film is performed by exposing the coating film to an environment in which the temperature condition is 50 to 100 ℃ and the relative humidity condition is 60 to 100% in an appropriate combination for a predetermined time. An example of a combination of the temperature condition and the relative humidity condition of the humidification treatment of the coating film is a temperature of 85 ℃ and a relative humidity of 85%.
In the optical filters 1a to 1d, the light absorbing layer 10 has a thickness of, for example, 400 μm or less, preferably 300 μm or less, and more preferably 250 μm or less. This makes it easy for the filters 1a to 1d to have desired optical characteristics. As described above, since the amount of the resin used can be suppressed to a small amount in the light absorbing composition, the thickness of the light absorbing layer 10 can be easily reduced by using the light absorbing composition. The small thickness of the light absorbing layer 10 is advantageous for reducing the height of the device on which the filters 1a to 1d are mounted. In the filters 1a to 1d, the light absorbing layer 10 has a thickness of, for example, 30 μm or more.
As shown in fig. 1, the optical filter 1a further includes a transparent dielectric substrate 20. The light absorbing layer 10 is formed in parallel with one main surface of the transparent dielectric substrate 20. The light absorbing layer 10 may be in contact with one main surface of the transparent dielectric substrate 20, for example. In this case, the light absorbing layer 10 is produced by forming a coating film of the light absorbing composition on one main surface of the transparent dielectric substrate 20 as described above.
The type of the transparent dielectric substrate 20 is not particularly limited as long as the normalized transmittance spectrum in the optical filter 1a satisfies the above-described conditions. According to circumstances, the transparent dielectric substrate 20 may have an absorption capability in the infrared region. The transparent dielectric substrate 20 may have an average spectral transmittance of 90% or more at a wavelength of 350nm to 900nm, for example. The material of the transparent dielectric substrate 20 is not limited to a specific material, and is, for example, a prescribed glass or resin. When the material of the transparent dielectric substrate 20 is glass, the transparent dielectric substrate 20 is, for example, transparent glass or infrared cut glass formed of silicate glass such as soda-lime glass or borosilicate glass. The infrared cut glass is, for example, a phosphate glass or a fluorophosphate glass containing CuO.
When the material of the transparent dielectric substrate 20 is a resin, the resin is, for example, a cyclic olefin resin such as a norbornene resin, a polyarylate resin, an acrylic resin, a modified acrylic resin, a polyimide resin, a polyetherimide resin, a polysulfone resin, a polyethersulfone resin, a polycarbonate resin, or a silicone resin.
The optical filter 1b according to another example of the present invention is configured similarly to the optical filter 1a, except for the case where it is specifically described. The description of the optical filter 1a also applies to the optical filter 1b, as long as there is no technical contradiction.
As shown in fig. 2, the filter 1b further includes an infrared-reflective film 30. The infrared reflection film 30 is a film formed by alternately laminating two or more materials having different refractive indices. The material for forming the infrared reflection film 30 is, for example, SiO2、TiO2And MgF2And the like, inorganic materials, and organic materials such as fluorine resins. The laminate provided with the infrared-reflective film 30 transmits light having a wavelength of 350nm to 800nm and reflects light having a wavelength of 850nm to 1200nm, for example. The laminate provided with the infrared-reflective film 30 has a spectral transmittance of, for example, 85% or more, preferably 90% or more at a wavelength of 350nm to 800nm, and has a spectral transmittance of, for example, 1% or less, preferably 0.5% or less at a wavelength of 850nm to 1200 nm. This enables the optical filter 1b to more effectively shield light having a wavelength in the range of 850nm to 1200nm or light having a wavelength in the range of 900nm to 1200 nm.
The method of forming the infrared reflective film 30 of the filter 1b is not particularly limited, and any of vacuum Deposition, sputtering, CVD (Chemical Vapor Deposition), and a sol-gel method using spin coating or spray coating may be used depending on the kind of material forming the infrared reflective film 30.
As shown in fig. 3, in an optical filter 1c according to another example of the present invention, the light absorbing layer 10 includes a first light absorbing layer 10a and a second light absorbing layer 10b separated by a transparent dielectric substrate 20. The first light absorbing layer 10a and the second light absorbing layer 10b are formed in parallel with one main surface of the transparent dielectric substrate 20, and are in contact with the transparent dielectric substrate 20. Thus, the thickness of the light absorbing layer necessary for obtaining desired optical characteristics of the filter 1c can be ensured by the two light absorbing layers. The first light absorbing layer 10a and the second light absorbing layer 10b may have the same thickness or different thicknesses. That is, the first light absorbing layer 10a and the second light absorbing layer 10b are formed so that the thickness of the light absorbing layer 10 necessary for obtaining desired optical characteristics of the optical filter 1c is distributed uniformly or unequally. Thus, the first light absorbing layer 10a and the second light absorbing layer 10b have relatively small thicknesses. Therefore, the thickness unevenness of the light absorbing layer, which is generated when the thickness of the light absorbing layer is large, can be suppressed. In addition, the time for coating the light absorbing composition can be shortened, and the time for drying the coating film of the light absorbing composition can be shortened. In the case where the transparent dielectric substrate is very thin, if the light absorbing layer is formed only on one main surface of the transparent dielectric substrate, there is a possibility that: the filter warps due to stress accompanying shrinkage generated when the light absorbing layer is formed from the light absorbing composition. However, by forming the light absorbing layers 10 on both main surfaces of the transparent dielectric substrate 20, the occurrence of warpage in the optical filter 1c can be suppressed even when the transparent dielectric substrate 20 is very thin.
As shown in fig. 4, a filter 1d according to another example of the present invention is constituted only by the light absorbing layer 10. The optical filter 1d can be produced by, for example, peeling off the light absorbing layer 10 formed on the substrate from the substrate. In this case, the material of the substrate is not limited to the transparent dielectric, and for example, a metal substrate may be used.
As shown in fig. 5, the imaging optical system 100 may be provided using, for example, a filter 1 a. The imaging optical system 100 may include, for example, an imaging lens 3 in addition to the filter 1 a. The imaging optical system 100 is disposed in front of the imaging element 2 in an imaging apparatus such as a digital camera. The imaging element 2 is a solid-state imaging element such as a CCD or a CMOS. As shown in fig. 5, light from a subject is condensed by the imaging lens 3, and light rays of a predetermined wavelength are cut by the filter 1a and enter the imaging element 2. The imaging optical system 100 may include any one of the filter 1b, the filter 1c, and the filter 1d instead of the filter 1 a.
Examples
The present invention will be described in more detail by way of examples. The present invention is not limited to the following examples. First, the evaluation methods of the optical filters of the examples and comparative examples will be described.
< measurement of thickness of light-absorbing layer >
The thicknesses of the optical filters of the examples and comparative examples were measured by a digital micrometer. In most embodiments, the thickness of the light absorbing layer of the filter is calculated by subtracting the thickness of the transparent glass substrate from the thickness of the filter. In example 35, the thickness of the light-absorbing layer was directly measured by a digital micrometer.
< measurement of transmittance Spectrum of optical Filter >
The transmittance spectra when light having a wavelength of 300nm to 1200nm was made incident on the filters of examples and comparative examples were measured using an ultraviolet-visible spectrophotometer (product name: V-670, manufactured by JASCO corporation). In this measurement, the incident angle of the incident light to the filter was set to 0 ° (degree).
< determination of normalized transmittance Spectrum >
The absorption characteristics of light in the optical filter, that is, the transmittance spectrum, change depending on the thickness of the light absorption layer in the optical filter. It is appropriate to prepare various samples, compare the performance of the samples, or adjust the preparation conditions, and normalize the measured transmittance spectrum of the filter based on some index to evaluate the transmittance spectrum. Therefore, the transmittance spectra of the optical filters of examples and comparative examples measured in the wavelength range of 300nm to 1200nm were normalized so that the spectral transmittance at a wavelength of 700nm was 20%, and the normalized transmittance spectra were determined. Specifically, the following calculations (1) to (4) were performed.
(1) In the transmittance spectra measured for the filters of examples and comparative examples, the spectral transmittance was multiplied by 100/92 for each wavelength to obtain a second spectral transmittance at which the reflection on both sides of the filter was substantially eliminated.
(2) In consideration of the fact that most of the optical filters of examples and comparative examples had transparent glass substrates (product name: D263 Teco, manufactured by SCHOTT Co., Ltd.) which did not substantially absorb light in the wavelength range of 350nm to 1200nm, the absorption coefficient of the light-absorbing layer for each wavelength was determined by the thickness of the light-absorbing layer in the optical filter and the second spectral transmittance.
(3) Next, it is calculated what spectral transmittance the optical filter having the light absorption layer having the absorption coefficient has for each wavelength when the thickness of the light absorption layer is changed. In this case, the spectral transmittance is calculated by multiplying 92/100 in advance to estimate the reflection on the filter surface. The thickness of the light-absorbing layer was determined so that the spectral transmittance at 700nm calculated in this manner was 20% (calculated thickness).
(4) Based on the calculated thickness of the light absorbing layer determined in the step (3), the spectral transmittances of the optical filters of the examples and comparative examples were obtained for each wavelength, and transmittance spectra were obtained. The transmittance spectrum is determined as a normalized transmittance spectrum.
< example 1>
Copper acetate monohydrate (1.125 g) and Tetrahydrofuran (THF) (60 g) were mixed and stirred for 3 hours to obtain solution A. Then, THF10g was added to 0.447g of phenylphosphonic acid and stirred for 30 minutes to obtain a solution B-1. Further, 10g of THF was added to 0.670g of 4-bromophenylphosphonic acid and the mixture was stirred for 30 minutes to obtain solution B-2. Next, the B-1 liquid and the B-2 liquid were mixed and stirred for 1 minute, 5.415g of methyltriethoxysilane (MTES; manufactured by shin-Etsu chemical Co., Ltd.) and 1.775g of tetraethoxysilane (TEOS; special grade manufactured by Kishida chemical Co., Ltd.) were added and further stirred for 1 minute to obtain a B liquid. While the solution A was stirred, the solution B was added to the solution A, and the mixture was stirred at room temperature for 1 minute. Then, 40g of toluene was added to the solution, and the mixture was stirred at room temperature for 1 minute to obtain solution C. This solution C was put into a flask, and heated in an oil bath (OSB-2100, model: manufactured by Tokyo chemical and mechanical instruments) while solvent removal treatment was carried out by a rotary evaporator (N-1110 SF, model: manufactured by Tokyo chemical and mechanical instruments). The oil bath was set to a temperature of 85 ℃. After that, the solution D after the solvent removal treatment was taken out from the flask. The liquid D as a dispersion of fine particles of copper phenyl phosphonate (light absorber) was transparent, and the fine particles were well dispersed.
Copper acetate monohydrate 0.450g and THF 24g were mixed and stirred for 3 hours to obtain solution E. Further, to 0.257g of n-butylphosphonic acid (manufactured by Nippon Chemical Co., Ltd.) was added 10g of THF and stirred for 30 minutes, and 2.166g of methyltriethoxysilane (MTES: manufactured by shin-Etsu Chemical Co., Ltd.) and 0.710g of tetraethoxysilane (TEOS: Special grade manufactured by Kishida Chemical Co., Ltd.) were added and stirred for further 1 minute to obtain solution F. While stirring solution E, solution F was added to solution E, and the mixture was stirred at room temperature for 1 minute. Then, 16G of toluene was added to the solution, and the mixture was stirred at room temperature for 1 minute to obtain solution G. The solution G was charged into a flask, and desolventization was performed by a rotary evaporator while heating the flask with an oil bath. The oil bath was set to a temperature of 85 ℃. Then, the H solution after the solvent removal treatment was taken out from the flask. The liquid H as a dispersion of fine particles of copper butylphosphonate (light absorber) was transparent, and the fine particles were well dispersed.
16g of silicone resin KR-311 (nonvolatile content: 60% by mass, manufactured by shin-Etsu chemical industries, Ltd.) and 4g of silicone resin KR-300 (nonvolatile content: 50% by mass, manufactured by shin-Etsu chemical industries, Ltd.) were mixed and stirred for 10 minutes to obtain a resin composition Y. The content of solid content (nonvolatile content) in the resin composition Y was determined from the relationship of 60 mass% × 16/20+50 mass% × 4/20 and found to be 58 mass%.
8.800g of the resin composition Y was added to the solution D and stirred for 5 minutes to obtain a solution I. To the obtained solution I, solution H was added and stirred for 10 minutes, to obtain a light absorbing composition of example 1. The mass-based and mass-based contents of the respective components in the light absorbing composition of example 1 are shown in tables 1 and 2, respectively. The content of the solid content of the alkoxysilane monomer is determined by converting the content of the alkoxysilane monomer into a hydrolyzed condensate of the alkoxysilane monomer.
The light absorbing composition of example 1 was applied to a transparent glass substrate (product name: D263T eco, manufactured by SCHOTT Co.) made of borosilicate glass having a size of 76mm × 76mm × 0.21mm in a range of 30mm × 30mm at the center of one main surface thereof using a dispenser to form a coating film. At this time, a frame having an opening corresponding to the application range of the light absorbing composition is placed on one main surface of the transparent glass substrate to prevent the light absorbing composition from flowing out. Subsequently, the transparent glass substrate having the undried coating film was put into an oven and dried at 85 ℃ for 6 hours to cure the coating film. Then, the transparent glass substrate having the coating film was left in a constant temperature and humidity chamber set at 85 ℃ and 85% relative humidity for 2 hours, and subjected to a humidification treatment to cut off a portion where the light absorbing layer having a certain thickness was formed, thereby producing the optical filter of example 1. The thickness of the light absorbing layer in the optical filter of example 1 was 158 μm. The normalized transmittance spectrum of the filter of example 1 is shown in fig. 6. In addition, the optical properties read from the normalized transmittance spectrum of the optical filter of example 1 are shown in table 7.
< other examples and comparative examples >
Light absorbing compositions of examples 2 to 63 and light absorbing compositions of comparative examples 1 to 12 were prepared in the same manner as in example 1 except that the contents of the respective components were adjusted to amounts shown in tables 1 to 6. The light absorbing compositions of examples 11, 36 and 37 contained methyltrimethoxysilane (MTMS) in place of MTES, and the light absorbing compositions of examples 12, 13, 38 and 39 contained dimethyldiethoxysilane (DMDES) in place of MTES. 8g of silicone resin KR-212 (nonvolatile content: 70% by mass, manufactured by shin-Etsu chemical industries, Ltd.) and 12g of silicone resin KR-300 (nonvolatile content: 50% by mass, manufactured by shin-Etsu chemical industries, Ltd.) were mixed and stirred for 10 minutes to obtain a resin composition X. Further, as Z, a silicone resin KR-5230 (produced by shin-Etsu chemical industries, Ltd., nonvolatile content: 60 mass%) was used. The content of the solid content in the resin composition X was determined in the same manner as in the resin composition Y and was 58% by mass. The content of the solid content in the resin composition Z was determined to be 60 mass%.
Optical filters of examples 2 to 63 were produced in the same manner as in example 1 except that the light absorbing compositions of examples 2 to 63 were used instead of the light absorbing composition of example 1. The optical filter of example 35 was produced by peeling the light-absorbing layer from the transparent glass substrate, and consisted of only the light-absorbing layer. Optical filters of comparative examples 1 to 4, 6 to 9 and 11 were produced in the same manner as in example 1 except that the light absorbing composition of comparative examples 1 to 4, 6 to 9 and 11 was used instead of the light absorbing composition of example 1.
Normalized transmittance spectra of the filters of examples 2 and 10 are shown in fig. 7 and 8. In addition, the optical properties read from the normalized transmittance spectra of the optical filters of examples 2 to 10 are shown in table 7. As shown in table 7, it can be seen that: within the specified range, the optical filter has good characteristics even if the addition amount of MTES and the addition amount of TEOS in the light absorbing composition are changed. The addition amount of the alkoxysilane monomer in the light absorbing composition of example 10 is about 6 times the addition amount of the alkoxysilane monomer in the light absorbing composition of example 2 on a mass basis. Therefore, even if the light absorbing composition contains relatively large amounts of alkoxysilane monomers exceeding the minimum necessary for dispersing the light absorbing agent, it is considered that the production of an optical filter having good optical characteristics is not an obstacle. This is considered to be related to the fact that the hydrolyzed condensate of alkoxysilane monomer has a skeleton similar to silicate glass based on siloxane bond (-Si-O-Si-) and has high transparency to visible light. One of the advantages of alkoxysilane monomers over other dispersants such as phosphate esters having polyoxyalkyl groups is that variations in the amount of addition in the light absorbing composition hardly affect the optical properties of the optical filter.
As shown in table 7, it is understood from the results of examples 1 to 10 regarding the optical filter that even when the kind and amount of the silicone resin are changed in the light absorbing composition, the optical filter having good optical characteristics can be produced.
< comparative examples 1 and 2>
The normalized transmittance spectrum of the filter of comparative example 2 is shown in fig. 9. Table 12 shows optical characteristics read from the transmittance spectrum of the filter of comparative example 1 and the normalized transmittance spectrum of the filter of comparative example 2.
In comparative example 1, the liquid containing the light absorber formed from the alkyl-based phosphonic acid and the copper ion was transparent, while the liquid containing the light absorber formed from the phenyl-based phosphonic acid and the copper ion was turbid. In addition, the filter of comparative example 1 was white-turbid, and the transmittance in the visible light region was significantly low in the filter of comparative example 1. It is believed that: this is because the content of the alkoxysilane monomer in the light absorbing composition is small.
In comparative example 2, the transparency of the liquid containing the light absorber composed of the alkyl phosphonic acid and the copper ion and the transparency of the liquid containing the light absorber composed of the phenyl phosphonic acid and the copper ion were high. However, the transmittance in the visible light region was low in the filter of comparative example 2. As suggested by the results of comparative example 2, the content of the alkoxysilane monomer in the light absorbing composition of comparative example 2 was slightly lower than the amount required to produce a filter having good optical characteristics.
< examples 11 to 13>
Normalized transmittance spectra of the filters of examples 11 and 12 are shown in fig. 10 and 11, respectively. The optical properties read from the normalized transmittance spectra of the optical filters of examples 11 to 13 are shown in table 8. The light absorbing composition of example 11 contains MTMS as the alkoxysilane monomer instead of MTES. MTES has 3 ethoxy groups, while MTMS has 3 methoxy groups. The content of MTMS in the light absorbing composition of example 11 was adjusted to be about the same as the content of MTES in the light absorbing composition of example 1 on a mass basis in terms of solid content of alkoxysilane monomer. As is clear from the results of example 11 in table 8, even when MTMS was used as the alkoxysilane monomer, optical filters having good optical characteristics could be produced. This indicates that there is room for various choices of the kind of alkoxy group in the alkoxysilane monomer in order to produce an optical filter having good optical characteristics.
The light absorbing compositions of examples 12 and 13 contain DMDES as the alkoxysilane monomer instead of MTES. The content of DMDES in the light absorbing compositions of examples 12 and 13 was adjusted to be about the same as the content of MTES in the light absorbing composition of example 1 on a mass basis in terms of solid content of alkoxysilane monomer. As is clear from the results in table 8 for examples 12 and 13, even when DMDES is used as the alkoxysilane monomer, an optical filter having good optical characteristics can be produced. DMDES has 2 methyl groups, and therefore they cause steric hindrance, and are expected to have advantageous effects as well as MTES. The expected effects were obtained in the filters of examples 12 and 13. From the results, it was revealed that the light absorbing agent can be dispersed appropriately regardless of the number of alkyl groups of the alkoxysilane monomer contained in the light absorbing composition.
< example 14>
The normalized transmittance spectrum of the filter of example 14 is shown in fig. 12. In addition, the optical properties read from the normalized transmittance spectrum of the optical filter of example 14 are shown in table 8. The light absorbing composition of example 14 contains MTES alone as the alkoxysilane monomer. From the results of example 14 in fig. 12 and table 8, the optical filter of example 14 had good optical characteristics. It is thus shown that it is not necessary to contain TEOS as the alkoxysilane monomer, and that it is advantageous to contain an alkoxysilane monomer having an alkyl group.
< comparative example 3>
The normalized transmittance spectrum of the filter of comparative example 3 is shown in fig. 13. Table 12 shows optical characteristics read from the normalized transmittance spectrum of the optical filter of comparative example 3. The content of the alkoxysilane monomer in the light absorbing composition of comparative example 3 is lower than the content of the alkoxysilane monomer in the light absorbing composition of example 14. The liquid containing the light absorber formed from the alkyl phosphonic acid and the copper ion and the liquid containing the light absorber formed from the phenyl phosphonic acid and the copper ion, which were prepared in order to obtain the light absorbing composition of comparative example 3, were high in transparency. However, the filter of comparative example 3 had a low transmittance in the visible light region and did not have good optical characteristics. It is suggested that the content of the alkoxysilane monomer in the light absorbing composition of comparative example 3 is slightly lower than the amount required to manufacture a filter having good optical characteristics.
< comparative example 4>
The optical properties read from the normalized transmittance spectrum of the filter of comparative example 4 are shown in table 12. As shown in table 5, in the light absorbing composition of comparative example 4, the solid content of MTES: the amount of solid components of TEOS was adjusted to about 1: 1. the content of the alkoxysilane monomer in the light absorbing composition of comparative example 4 is adjusted to be about the same as the content of the alkoxysilane monomer in the light absorbing composition of example 2 on a mass basis in terms of the solid content of the alkoxysilane monomer. In the filter of comparative example 4, the transmittance in the visible light region was low. It is believed that: the reason for this is that the alkoxysilane monomer cannot sufficiently exert a function of suppressing aggregation of the light absorbing agent. From the results, it is understood that the addition amount of the alkoxysilane monomer having an alkyl group contributes more favorably to the light absorbing composition in terms of imparting good characteristics to the optical filter than the addition amount of the alkoxysilane monomer and the amount of the final solid content thereof. This suggests that the optical filter can exhibit good characteristics due to steric hindrance caused by the methyl group of MTES.
< example 15>
The optical properties read from the normalized transmittance spectra of the filter of example 15 are shown in table 8. As shown in table 1, in the light absorbing composition of example 15, the solid content of MTES: the amount of solid components in TEOS was adjusted to be about 1: 1. the content of the alkoxysilane monomer in the light absorbing composition of example 15 is adjusted to be about the same as the content of the alkoxysilane monomer in the light absorbing composition of example 1 on a mass basis in terms of the solid content of the alkoxysilane monomer. As shown in table 8, the optical filter of example 15 had good optical characteristics. It is considered that the content of MTES in the light absorbing composition of example 15 is sufficient to prevent aggregation of the light absorbing agent, which results in a difference in the optical characteristics of the optical filter of example 15 and the optical characteristics of the optical filter of comparative example 4.
< examples 16 and 17>
The normalized transmittance spectrum of the filter of example 16 is shown in fig. 14. In addition, the optical properties read from the normalized transmittance spectra of the filters of examples 16 and 17 are shown in table 8. As shown in table 1, in the light absorbing compositions of examples 16 and 17, the solid content of MTES was: the amount of solid components of TEOS was adjusted to about 3: 7. in addition, the amount of solid components of the alkoxysilane monomer in the light absorbing compositions of examples 16 and 17 is greater than that in the light absorbing composition of example 1. As shown in table 8, the optical filters of examples 16 and 17 had good optical characteristics. When compared with the results of comparative examples 2 and 4 with respect to the light absorbing compositions, it is suggested that the content of MTES in the light absorbing compositions of examples 16 and 17 is sufficient to prevent aggregation of the light absorbing agent.
< comparative example 5>
As shown in table 5, the light absorbing composition of comparative example 5 contained only TEOS as an alkoxysilane monomer. The light absorbing composition of comparative example 5 had a relatively high TEOS content, but the light absorbing composition of comparative example 5 was turbid and no suitable filter could be obtained.
< examples 18 and 19>
The normalized transmittance spectrum of the filter of example 18 is shown in fig. 15. In addition, the optical properties read from the normalized transmittance spectra of the filters of examples 18 and 19 are shown in table 8. The content of the phenyl phosphonic acid in the light absorbing compositions of examples 18 and 19 was adjusted to be the same as that of the phenyl phosphonic acid in the light absorbing compositions of examples 1 to 17 on a substance basis. However, in the light absorbing compositions of examples 18 and 19, only phenylphosphonic acid was contained as the phenyl phosphonic acid. As shown in table 8, the optical filters of examples 18 and 19 had good optical characteristics. From this fact, it is found that an optical filter having excellent optical characteristics can be produced by including a phenyl phosphonic acid containing no halogenated phenylphosphonic acid and a butylphosphonic acid in the light absorbing composition.
< examples 20 and 21>
The normalized transmittance spectrum of the filter of example 20 is shown in fig. 16. In addition, the optical properties read from the normalized transmittance spectra of the filters of examples 20 and 21 are shown in table 8. As shown in table 2, in the light absorbing compositions of examples 20 and 21, the content of phenylphosphonic acid: the content of bromophenylphosphonic acid was adjusted to about 3: 7. as shown in table 8, the optical filters of examples 20 and 21 had good optical characteristics. In the light absorbing composition of example 1, the content of phenylphosphonic acid: the bromophenylphosphonic acid content is about 1: 1. from the results concerning examples 20 and 21, it is understood that the optical filter has good optical characteristics even if the ratio of the content of phenylphosphonic acid to the content of bromophenylphosphonic acid in the light absorbing composition is varied.
< examples 22 and 23>
The normalized transmittance spectrum of the filter of example 22 is shown in fig. 17. In addition, the optical properties read from the normalized transmittance spectra of the filters of examples 22 and 23 are shown in table 8. In the light absorbing compositions of examples 22 and 23, chlorophenylphosphonic acid was contained instead of bromophenylphosphonic acid contained in the light absorbing composition of example 1. As shown in table 8, the optical filters of examples 22 and 23 had good optical characteristics. From this, it is found that an optical filter having excellent optical characteristics can be produced regardless of the type of the halogenated phenylphosphonic acid contained in the light absorbing composition.
< examples 24 to 49 and comparative examples 6 to 10>
The normalized transmittance spectrum of the filter of example 24 is shown in fig. 18. In addition, the optical properties read from the normalized transmittance spectra of the filters of examples 24 to 49 are shown in tables 9 and 10. Further, the optical properties read from the transmittance spectra or normalized transmittance spectra of the optical filters of comparative examples 6 to 9 are shown in table 12. The light absorbing compositions of examples 1 to 23 and comparative examples 1 to 5 were prepared by adding both phenyl phosphonic acid and alkyl phosphonic acid. On the other hand, the light absorbing compositions of examples 24 to 49 and comparative examples 6 to 10 were prepared by adding only phenyl phosphonic acid as phosphonic acid. As shown in tables 1 to 6, 9, 10, and 12, it was found that when the light absorbing composition contains a predetermined amount of the alkoxysilane monomer having an alkyl group, an optical filter having good optical characteristics can be produced. The light absorbing composition of comparative example 10 was turbid, and a suitable filter could not be obtained.
< examples 34 and 35>
Normalized transmittance spectra of the filters of examples 34 and 35 are shown in fig. 19 and 20, respectively. In addition, the optical properties read from the normalized transmittance spectra of the filters of examples 34 and 35 are shown in table 9. As shown in table 3, the light absorbing compositions of examples 34 and 35 were prepared without adding the resin composition containing a silicone resin. From the results of examples 34 and 35, it is understood that an optical filter having good optical characteristics can be produced without adding a resin composition containing a silicone resin to the light absorbing composition. This suggests that the hydrolyzed and condensed product of the alkoxysilane monomer contained in the light absorbing composition forms strong siloxane bonds (-Si-O-Si-), and that the hydrolyzed and condensed product effectively fills the gaps between the light absorbing agents and thereby functions to form the light absorbing layer. Therefore, it is considered that the inclusion of the alkoxysilane monomer in the light-absorbing composition is advantageous not only in appropriately dispersing the light-absorbing agent but also in forming the skeleton of the light-absorbing layer.
As described above, the optical filter of example 35 is constituted only by the light absorbing layer. As is clear from the results of example 35, when the alkoxysilane monomer is sufficiently contained in the light absorbing composition, the phosphate ester and the silicone resin are not required, and the optical filter not requiring the substrate can be manufactured. In other words, the alkoxysilane monomer can play a role of the phosphate ester, the silicone resin, and the transparent glass substrate alone.
< examples 50 to 63 and comparative examples 11 and 12>
The normalized transmittance spectrum of the filter of example 50 is shown in fig. 21. In addition, the optical properties read from the normalized transmittance spectra of the optical filters of examples 50 to 63 are shown in Table 11. Table 12 shows optical characteristics read from the normalized transmittance spectrum of the optical filter of comparative example 11. The light absorbing compositions of examples 1 to 23 and comparative examples 1 to 5 were prepared by adding both phenyl phosphonic acid and alkyl phosphonic acid. In contrast, the light absorbing compositions of examples 50 to 63 and comparative examples 11 and 12 were prepared using only an alkyl phosphonic acid as the phosphonic acid. The light absorbing composition of comparative example 12 was cloudy and no suitable optical filter could be obtained. As shown in tables 3 to 6, 11, and 12, it was found that when the light absorbing composition contains a predetermined amount of the alkoxysilane monomer having an alkyl group, an optical filter having good optical characteristics can be produced.
As is clear from the comparison between examples 1 to 23 and comparative examples 1, 2 and 4, in the case of the following (I), in order to provide the optical filter with good optical characteristics, the ratio of the content of the 2-functional or 3-functional alkoxysilane monomer having an alkyl group to the content of copper ions is preferably 2.5 or more on a substance basis.
(I) The light absorbing composition contains a phenyl phosphonic acid and an alkyl phosphonic acid, and contains a 4-functional alkoxysilane monomer and a 2-functional alkoxysilane monomer or a 3-functional alkoxysilane monomer.
As is clear from the comparison between examples 24 to 49 and comparative examples 6, 7, 9 and 10, in the case of the following (II), in order to provide the optical filter with good optical characteristics, the ratio of the content of the 2-functional or 3-functional alkoxysilane monomer having an alkyl group to the content of copper ions is preferably 2.5 or more on a substance basis.
(II) the light absorbing composition contains a phenyl phosphonic acid and does not contain an alkyl phosphonic acid, and contains a 4-functional alkoxysilane monomer and a 2-functional alkoxysilane monomer or a 3-functional alkoxysilane monomer.
As is clear from the comparison between examples 50 to 63 and comparative examples 11 and 12, in the case of the following (III), in order to provide a filter having good optical characteristics, the ratio of the content of the 2-functional or 3-functional alkoxysilane monomer having an alkyl group to the content of copper ions is preferably 1.5 or more on a substance basis.
(III) the light absorbing composition contains an alkyl phosphonic acid and does not contain a phenyl phosphonic acid, and contains a 4-functional alkoxysilane monomer and a 2-functional alkoxysilane monomer or a 3-functional alkoxysilane monomer.
Claims (9)
1. A light absorbing composition comprising:
a light absorber formed of a phosphonic acid represented by the following formula (a) and copper ions; and
an alkoxysilane monomer for dispersing the light absorbing agent,
does not contain a phosphate ester having a polyoxyalkyl group,
the alkoxysilane monomer is contained so that the normalized transmittance spectrum has a wavelength band having a spectral transmittance of 70% or more at a wavelength of 300 to 700nm and the difference between the maximum value and the minimum value of the wavelength in the wavelength band is 100nm or more,
the normalized transmittance spectrum is obtained as follows: a transmittance spectrum is obtained by vertically allowing light having a wavelength of 300 to 1200nm to enter a light absorbing layer formed by drying and humidifying a film of the light absorbing composition, and the normalized transmittance spectrum is obtained by normalizing the transmittance spectrum so that the spectral transmittance at a wavelength of 700nm is 20%,
[ CHEM 1 ]
In the formula, R11Is an alkyl group, an aryl group, a nitroaryl group, a hydroxyaryl group, or a haloaryl group in which at least 1 hydrogen atom in the aryl group is substituted with a halogen atom.
2. The light absorbing composition according to claim 1, wherein the alkoxysilane monomer comprises an alkyl group-containing alkoxysilane monomer represented by the following formula (b),
(R2)n-Si-(OR3)4-n(b)
in the formula, R2Is an alkyl group having 1 to 4 carbon atoms, R3Is an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 3.
3. The light absorbing composition of claim 2, wherein the phosphonic acid comprises R of formula (a)11Phosphonic acid which is an aryl, nitroaryl, hydroxyaryl or haloaryl in which at least 1 hydrogen atom of the aryl group is replaced by a halogen atom,
the alkoxysilane monomer includes the alkyl group-containing alkoxysilane monomer of the formula (b) in which n ═ 1 or 2, and a tetrafunctional alkoxysilane monomer represented by the following formula (c),
wherein the ratio of the content of the alkyl group-containing alkoxysilane monomer of the formula (b) in which n is 1 or 2 to the content of the copper ion is 2.5 or more on a substance basis,
Si-(OR4)4(c)
in the formula, R4Is an alkyl group having 1 to 8 carbon atoms.
4. An optical filter comprising a light-absorbing layer containing a light-absorbing agent comprising a phosphonic acid represented by the following formula (a) and copper ions and a hydrolyzed polycondensate of alkoxysilane monomers and not containing a phosphate having a polyoxyalkyl group,
the normalized transmittance spectrum has a first wavelength band having a spectral transmittance of 70% or more at a wavelength of 300nm to 700nm, and the difference between the maximum value and the minimum value of the wavelength in the first wavelength band is 100nm or more,
the normalized transmittance spectrum is obtained as follows: obtaining a transmittance spectrum by perpendicularly allowing light having a wavelength of 300 to 1200nm to enter the filter, normalizing the transmittance spectrum so that the spectral transmittance at a wavelength of 700nm is 20%, thereby obtaining the normalized transmittance spectrum,
[ CHEM 2 ]
In the formula, R11Is an alkyl group, an aryl group, a nitroaryl group, a hydroxyaryl group, or a haloaryl group in which at least 1 hydrogen atom in the aryl group is substituted with a halogen atom.
5. The optical filter according to claim 4, wherein the normalized transmittance spectrum has a second wavelength band having a spectral transmittance of 80% or more at a wavelength of 300nm to 700nm, and a difference between a maximum value and a minimum value of the wavelength in the second wavelength band is 40nm or more.
6. The optical filter according to claim 4 or 5, wherein the normalized transmittance spectrum has a third band having a spectral transmittance of 20% or less at a wavelength of 700nm to 1200nm, and a difference between a maximum value and a minimum value of the wavelength in the third band is 120nm or more.
7. A filter according to any one of claims 4 to 6 in which the normalised transmittance spectrum has a fourth wavelength band in which the spectral transmittance decreases with increasing wavelength and a fifth wavelength band which is a band containing wavelengths shorter than the minimum of the wavelengths in the fourth wavelength band in which the spectral transmittance increases with increasing wavelength,
the spectral transmittance in the fourth wavelength band shows that the wavelength of 50%, i.e., the first cut-off wavelength, exists in the range of 600nm to 650nm,
a wavelength at which the light transmittance in the fifth wavelength band is 50%, that is, a second cut-off wavelength, exists in a range of 350nm to 420nm,
the difference obtained by subtracting the second cut-off wavelength from the first cut-off wavelength is 200nm to 290 nm.
8. The optical filter according to any one of claims 4 to 7, wherein in the normalized transmittance spectrum, a maximum wavelength which is a wavelength showing a maximum spectral transmittance is present in a range of 500nm to 550nm, and a minimum wavelength which is a wavelength showing a minimum spectral transmittance in a range of 700nm to 1200nm is present in a range of 750nm to 900nm,
the difference obtained by subtracting the maximum wavelength from the minimum wavelength is 240 nm-360 nm.
9. The optical filter according to any one of claims 4 to 8, wherein a difference obtained by subtracting a minimum spectral transmittance at a wavelength of 700nm to 1200nm of the normalized transmittance spectrum from a maximum spectral transmittance in the normalized transmittance spectrum is 68% or more.
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| TWI799458B (en) | 2023-04-21 |
| JPWO2019093076A1 (en) | 2019-11-14 |
| US12071542B2 (en) | 2024-08-27 |
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| KR102465624B1 (en) | 2022-11-10 |
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| US20200270455A1 (en) | 2020-08-27 |
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| JP6734442B2 (en) | 2020-08-05 |
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